Dental milling blank for the production of permanent indirect restorations and computer-aided process for producing the permanent indirect restorations

ABSTRACT

A dental milling blank for the production of permanent indirect restorations in the CAD/CAM process, characterized in that it has a water sorption WSP of less than/equal to 18 μg/mm3, measured according to ISO 4049 and an E modulus E greater than/equal to 13 GPa, measured according to the ADA specification No. 27 and a quotient Q of WSP/E of less than 1.35 μg/(GPa×mm3) and consists of the polymerization product of a radically curable dental composition, which comprisesa) inorganic fillers, wherein the total mass of the inorganic fillers is at least 83 wt. %, based on the total mass of the composition,b) radically polymerizable monomers,c) one or more initiators for radically curing.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/897,777, filed Feb. 15, 2018, which claims priority to GermanApplication No. 10 2017 103084.0 filed Feb. 15, 2017, the entireties ofwhich are incorporated herein by reference.

The present invention relates to dental milling blanks based on plastic,so-called composite blocks, for the production of dental prostheses in aCAD/CAM process. Prosthetic restorations form a replacement for teethand for example include crowns and bridges, partial crowns, inlays,onlays or veneers.

Technical progress with computer-controlled machines has been attendedby the development of milling machines which, in a very short time andat minimal cost, are capable of producing prosthetic restorations withunheard-of precision. Against this background, so-called “digitaldentistry” has developed. Today it is of outstanding importance indental technology.

Initially, only ceramic or metallic materials were milled, however, asthe dental composite materials became ever better matched to the hardtooth tissue, this substance class also became of interest for use as amilling blank.

Unlike composite materials, which by specific formulation of resinmatrix and filler composition can be adapted to the manifoldrequirements for a dental material in the hostile environment of theoral cavity, ceramic materials can have too high a degree of hardnessand because of their inherent brittleness have a tendency to fracture.Metallic materials are poorly acceptable for aesthetic reasons, andoften cause allergic reactions in patients.

The present invention relates to a high performance composite block forthe production of permanent indirect restorations in the CAD/CAMprocess. A dental composite material is understood by those skilled inthe art to be a radically polymerizable or radically polymerizedcomposition which contains at least one radically polymerizable liquidor one radically polymerized solid resin phase, a solid phase,comprising fillers in a great diversity of types and quantities, one ormore polymerization initiator(s) and optionally common additives such asinhibitors, dyes, stabilizers, etc. The not yet radically-curedcomposite material can be radically polymerized either chemically and/orthermally and/or photochemically by irradiation.

Dental composite blocks, or dental milling blanks, are known from theprior art.

DE 699 22 413 T2 describes a cuttable blank which contains a polymerresin and a finely divided filler material with a maximum particlediameter of less than 50 micrometers. The resin phase of the dentalcompositions studied in this document comprises the system bis-GMA(2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane)/TEGDMA(triethylene glycol dimethacrylate), the filler phase containssurface-silanized silicic acid and glass.

EP 3 050 533 A1 discloses dental resin blocks which use as the resinphase UDMA/TEGDMA (urethane dimethacrylate/triethylene glycoldimethacrylate) 80/20, UDMA/bis-MEPP/HDP (urethanedimethacrylate/2,2-bis(4-methacryloxypolyethoxyphenyl)propane/2-hydroxy-1,3-dimethacryloxypropane60/20/20 and 50/30/20 and UDMA/bis-MEPP (urethanedimethacrylate/2,2-bis(4-methacryloxypolyethoxyphenyl)propane 60/40.Unfortunately it is not clear from the document which urethanedimethacrylate is used. According to an older examined and publishedapplication (DE 26 56 847) by the same applicant, the degree ofethoxylation of the bis-MEPP lies in the range from 2.2 to 6. This meansthat for the production of the bis-MEPP the bisphenol A is reacted with2.2 to 6 moles of ethylene oxide and finally this intermediate productis saturated with 2 moles of methacrylic acid. These resin compositionsare mixed with inorganic fillers to give radically curable pastes infiller to resin weight ratios from 64:36 to 70.8:29.2 and then thermallypolymerized to resin blocks by means of BPO (benzoyl peroxide).

DE 24 62 271 C2 claims dental molded bodies containing at least onepolymerized acrylate or methacrylate and a silanized microfine inorganicfiller based on silicon dioxide, which are characterized in that as thepolymerized acrylate or methacrylate they contain a polymerizationproduct of bis-GMA or another derivative of bisphenol A or a reactionproduct from hydroxyethyl methacrylates and diisocyanates, optionallytogether with polymerization products of short-chain methacrylate estersand/or bifunctional acrylate or methacrylate esters and as the inorganicfiller exclusively microfine silicon dioxide with a particle size from10 to 400 nm and with a BET surface area of less than 200 m²/g in aquantity from 20 to 80%, based on the weight of the material. Thequantity of the microfine silicic acid can lie in the range between 40to 75 weight percent, based on the molded bodies.

EP 2 623 065 B1 discloses blanks for a dental mill which target highmechanical properties such as flexural strength and gloss stability.These properties are achieved by means of a blank for a dental millwhich is formed from a cured product from a curable composition andcomprises: (a) a polymerizable monomer; (b) a spherical inorganic fillerwhich has an average primary particle size of not less than 0.1 μm andless than 1 μm and (c) an inorganic ultrafine particle aggregate filler,consisting of aggregates of inorganic ultrafine particles which have anaverage primary particle size from 2 to 50 nm. As the resin matrix, amonomer mixture of bis-GMA/TEGDMA/bis-MEPP(2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]propaney(triethylene glycoldimethacrylate)/2,2-bis(4-methacryloxypolyethoxy-phenyl)propane in theweight ratio 20/30/50 is used here.

WO 2011/087832 A1 relates to thermally cured composite blanks whichshould have significantly improved mechanical and esthetic properties.The radically curable compositions contain initiators which thermallydecompose. Since the decomposition takes place at higher temperatures,monomers are prevented from gelling prematurely under normal processingconditions and discoloring the blank because of degradation processes.

WO 2016/140950 A1 describes composite materials which in the cured statecan also be used as dental milling blanks. The compositions contain acurable resin component, ceramic fibers and filler in the form ofnanoclusters. The polymers should yield highly esthetic restorations andhave excellent polishability and polish retention properties. In apractical example, the composition of a resin phase is stated, whosecomponents bis-GMA, TEGDMA, UDMA, bisEMA-6 (ethoxylated bisphenol Adimethacrylate with 6 ethoxy groups) and PEG600DM (polyethylene glycoldimethacrylate with a molecular weight of the polyethylene units of ca.600 g/mol) is used in weight ratios of 25/1.2/35/35/3.8.

EP 2 881 077 A1 relates to milling blanks which should have excellentmechanical properties, excellent abrasion resistance and excellentsurface gloss. Here, these properties are to be achieved via processtechnology. In contrast to the conventional production methods, in whichthe composite material is processed by homogeneous mixing and kneadingof a curable monomer mixture with a filler into a paste which must havea certain flowability in order to be cured to a milling blank in a mold,this application proposes hot-pressing the inorganic filler in order toaggregate it and finally infiltrating it with the curable resin. Theresin should thus fill the interstitial spaces of the primary particlesand can then be cured. This process should allow the production ofblanks in which the filler particles lie closer to one another than ispossible in the conventional production process and thus make itpossible to provide milling blanks with a particularly high fillercontent.

U.S. Pat. No. 6,345,984 B2 relates to milling blanks wherein thecomposite material contains a particulate filler in a size range fromabout 0.1 to 5.0 μm and colloidal silicate at a size of 1 to about 70 nmand a resin phase of ethoxylated BPA (bisphenol A) dimethacrylate andthe degree of ethoxylation ranges from 1 to 20, preferably from 2 to 7moles ethylene oxide/mole BPA. The milling blank overall consists of ca.20 to ca. 30 wt. % of an organic matrix and ca. 65 to ca. 85 wt. %particulate filler, wherein the organic matrix consists of ca. 65 to ca.90 wt. % ethoxylated BPA dimethacrylate and of ca. 10 to ca. 30 wt. % ofa methacrylate oligomer, for example a polycarbonate dimethacrylatecondensation product. Taking account of U.S. Pat. No. 4,544,359, citedin U.S. Pat. No. 6,345,984 B2, this typical composition of a millingblank then appears as follows: particulate filler (0.1 to 5 μm) 65 to 79wt. %, colloidal silicate (1 to 70 nm) 1 to 5 wt. % and organic matrix20 to 30 wt. %.

U.S. Pat. No. 6,186,790 shows finished dental bridge elements, whereinthe composite material is fiber-reinforced.

DE 198 23 530 B4 relates to a dental resin material which is shaped intoa dental prosthesis by milling, which comprises an acrylic resin polymerwhich contains 20 to 70 wt. % of an inorganic filler with an averageparticle size from 10 to 40 nm in diameter, 1 to 40 wt. % of a glasspowder with an average particle size from 0.1-5 μm in diameter and 1-40wt. % of an organic-inorganic composite filler, which is produced bymixing and curing a mixture of an ultrafine inorganic filler with anaverage particle size from 10 to 40 nm in diameter and a methacrylate oracrylate monomer with at least one unsaturated double bond andpulverizing the cured mixture such that it has an average particle sizefrom 5 to 50 μm in diameter, wherein the acrylic resin polymer comprisesa combination of a methacrylate or acrylate monomer with at least oneunsaturated double bond and a thermal polymerization initiator. Inexample 5, the composite composition of a milling blank is described.The resin phase comprises UDMA/bis-MEPP in a weight ratio of 5/20 andthe solid phase contains 22 wt. % inorganic filler (for example Aerosilwith an average particle size from 10 to 40 nm), for example OX-50 (with40 nm primary particle size), 23 wt. % quartz glass powder (averageparticle size: 0.5 μm) and 30 wt. % barium glass powder (averageparticle size: 0.5 μm).

DE 601 11 868 T2 claims dental composites for making crowns, coatings,direct fillings, inlays, onlays and splints. The dental compositionscontain a polymerizable resin and 11 to 80 vol. % filler, whichessentially consists of a ground structural filler and a nanofiller,wherein the ground structural filler makes up between 10 vol. % and 70vol. % of the composite and consists of ground particles with an averageparticle size between 0.05 and 0.5 μm and wherein the ground structuralfiller contains less than 50 vol. % of particles over 0.5 μm in diameterand wherein the nanofiller makes up between 1.0 and 15 vol. % of thecomposite and essentially consists of discrete, non-aggregated particleswith an average particle size of less than 100 nm. In the examples, thetotal filler content in wt. % lies between 75 and 82.4 wt. %. Resin 1comprises bis-GMA/TEGDMA and ethoxylated BPA dimethacrylate with 3.5ethoxy groups per molecule in the weight ratio 3.0/25/72. Resin 2contains ethoxylated BPA dimethacrylate with 2.0 ethoxy groups permolecule and HEDMA in the weight ratio 90/10.

In U.S. Pat. No. 5,962,550, a resin-modified glass ionomer cement isdisclosed as a direct filling material, as core build-up material and asa sealing material for pits and fissures. Within the experimental bindercompositions studied, this system inter alia contains the followingparts by weight in the resin phase: bis-MEPP/UDMA/HEMA (hydroxyethylmethacrylate) 45/45/10, bis-MEPP/UDMA/BG (butanediol dimethacrylate)45/45/10, bis-MEPP/UDMA/TEGDMA 33/38/29, and bis-MEPP/UDMA/HEMA20/46/34.

U.S. Pat. No. 4,616,073 describes highly fluorinated methacrylateprepolymers which are used in non-hydroxylated bis-GMA systems andshould be suitable for use as sealing material and cement. Thesehydrophobic compositions should as far as possible not be sensitive tochemical softening or chemical degradation. Furthermore, they shouldexhibit little polymerization shrinkage and low water sorption. In theexamples, there are filler-free compositions in which the bis-EMA(2,2-bis[(methacryloxyethyloxy)phenyl]propane) with 2 ethoxy groups isused together with DMDMA (1,10-decamethylene dimethacrylate), PDFOMA(pentadecafluorooctyl methacrylate) and BDMA(p-tert.-butyl-N,N-dimethylaniline) in weight ratios44.31/44.31/11.15/0.23 and 44.25/44.25/11.15/0.35 and49.25/41.25/9.30/0.20 and 45.91/45.91/7.98/0.20. In thefiller-containing compositions, the bis-EMA is used in quantities of 10and 5.8 wt. % (mold No. 5 and 10B).

Inter alia, U.S. Pat. No. 6,030,606 also relates to cured products suchas crowns, bridges, inlays, onlays and implants. The compositionsaccording to the invention, which should have an excellent propertyprofile such as high material strength and hardness, contain 10-30% of aresin component, which comprises:

15 to 45% bisEMA6, 15 to 45% UDMA, 10 to 40% bis-GMA and 0 to 10%TEGDMA. The number of ethoxy groups in the bisEMA6 should lie between 5and 8, preferably about 6.

DE 10 2015 220 373 A1 discloses both curable and also cured dentalmaterials and also claims milling blanks. The compositions describedhere comprise a bimodal glass composition.

In the prior art concerning milling blanks, work is targeted above allon the mechanical properties such as flexural strength and hardness andon the esthetic aspects of the blanks.

In spite of major advances in materials development, increasinglygreater demands are being made on modern dental restorative materials.This applies to both the direct filling materials and also indirectmaterials such as for example CAD/CAM-produced restorations. In additionto increasing esthetic demands for example in terms of color,translucency/opacity and opalescence of the milling blanks, there arealso more stringent requirements regarding the physical properties. Thusinter alia the materials should have high strength, low abrasion, goodX-ray opacity and low water sorption.

The water sorption in particular can lead to a great variety ofproblems. Thus, as a rule, in case of high water sorption, increaseddiscolorations occur, since colored substances are often also absorbedwith the water. Apart from this esthetic aspect, however, as a result ofincreased water sorption the ester bonds of the radically cured resinmatrix may be hydrolytically cleaved and thus mechanical parameters suchas strength and abrasion resistance be reduced.

The stress arising in the material is generally described by the stresstensor (σ_(ij)) and the resulting deformation by the strain tensor(ε_(kl)). Both are second order tensors.

$\begin{matrix}{\sigma_{ij} = {{\begin{bmatrix}\sigma_{11} & \sigma_{12} & \sigma_{13} \\\sigma_{21} & \sigma_{22} & \sigma_{23} \\\sigma_{31} & \sigma_{32} & \sigma_{33}\end{bmatrix}\mspace{14mu} ɛ_{kl}} = \begin{bmatrix}ɛ_{11} & ɛ_{12} & ɛ_{13} \\ɛ_{21} & ɛ_{22} & ɛ_{23} \\ɛ_{31} & ɛ_{32} & ɛ_{33}\end{bmatrix}}} & (1)\end{matrix}$

The stress tensor is combined with the strain tensor via the elasticitytensor (E_(ijkl)), wherein the elasticity tensor is a fourth ordertensor with 81 components (i,j,k,l=1, . . . , 3).σ_(ij) =E _(ijkl)ε_(kl)  (2)

However, due to the symmetry of stress and strain tensor, the number ofthe independent components of E_(ijkl) after transformation into E_(IJ)decreases to 36. Thus the elasticity constant can be represented in a6×6 matrix and the stress and the strain each as six-component vectors.

$\begin{matrix}{\begin{bmatrix}\sigma_{1} \\\sigma_{2} \\\sigma_{3} \\\sigma_{4} \\\sigma_{5} \\\sigma_{6}\end{bmatrix} = {\begin{bmatrix}E_{11} & E_{12} & E_{13} & E_{14} & E_{15} & E_{16} \\E_{21} & E_{22} & E_{23} & E_{24} & E_{25} & E_{26} \\E_{31} & E_{32} & E_{33} & E_{34} & E_{35} & E_{36} \\E_{41} & E_{42} & E_{43} & E_{44} & E_{45} & E_{46} \\E_{51} & E_{52} & E_{53} & E_{54} & E_{55} & E_{56} \\E_{61} & E_{62} & E_{63} & E_{64} & E_{65} & E_{66}\end{bmatrix}\begin{bmatrix}ɛ_{1} \\ɛ_{2} \\ɛ_{3} \\ɛ_{4} \\ɛ_{5} \\ɛ_{6}\end{bmatrix}}} & (3)\end{matrix}$

Thus, in simple terms, the relationship between the stress (σ) arisingfrom water sorption and the resulting deformation ε (swelling) emergesvia the elastic modulus (E) as a proportionality constant:

$\begin{matrix}{\sigma = {E\; ɛ\mspace{14mu}{or}}} & (4) \\{ɛ = \frac{\sigma}{E}} & (5)\end{matrix}$

From this it emerges that a material with a high elastic modulus isbetter able to counteract stresses occurring, so that with the samestress a smaller deformation results.

It has now been found that for cured dental composites the deformation(swelling) occurring is proportional to the water sorption (W_(SP)) andmoreover inversely proportional to the elastic modulus. This means thatthe stress occurring is proportional to the water sorption.

$\begin{matrix}{ɛ \sim \sigma \sim {W_{SP}\mspace{14mu}{and}}} & (6) \\{ɛ \sim \frac{1}{E}} & (7) \\{ɛ \sim \frac{W_{SP}}{E}} & (8)\end{matrix}$

FIG. 1 shows the diagram of the quotient of water sorption/elasticmodulus against the linear swelling for experimental milling blanks.

FIG. 2 shows the diagram of the quotient of water sorption/elasticmodulus against the linear swelling for commercial milling blanks.

FIG. 3 shows the representation of an idealized crown for thedetermination of the linear swelling.

From FIGS. 1 and 2, a good correlation emerges between this quotient andthe linear swelling. The data from these diagrams derive from theexamples (see experimental section).

In particular, it is surprising that the proportionality exists notsimply between the swelling and the water sorption, but rather betweenthe swelling and the quotient of water sorption and elastic modulus.Thus, with equal water sorption, materials with different elastic modulidisplay different degrees of swelling.

However, the above finding of a strict proportionality between watersorption and swelling (with constant E modulus) is itself surprising, inthat the phenomenon here discovered for the first time cannot beexplained solely by the volume of the absorbed water molecules in thepolymer, since analogous experiments with organic solvents instead ofwater showed no proportionality between their sorption and swelling ofthe material. Presumably, the water molecules have a destructive effecton existing superstructures such as the secondary or tertiary structurein the polymer. Under the extreme conditions in the oral environment,particularly under the constant influence of saliva, water sorption bythe finished restoration takes place. Water molecules embed themselvesin the polymer network, form hydrogen bridge bonds there, claim spacefor themselves and disturb established superstructures. This results instresses in the material. On the microscopic scale, broadening of thepolymer network, and on the macroscopic scale swelling of therestoration results.

For example, the swelling of a crown leads to an increase in theexternal and internal diameter, since the whole restoration expands dueto the swelling. Here the relative linear swelling (in percent) is aboutone third of the relative volume swelling (in percent). By increasingthe internal diameter, a tensile force arises, which is exerted on theadhesive bond of the luted crown. If the tensile forces locally exceedthe adhesion, breaking away of the luting material and marginal gapformation results. These sites involve an increased risk of colonizationby bacteria and the formation of secondary caries. If the swelling islarge enough or the continuing loading of the defect sites formed ishigh enough, total loss of retention of the restoration occurs.

Restorations produced from composite milling blanks are adhesivelyluted. During this, the stresses arising due to the swelling aretransferred via the luting composite onto the adhesive bond to the toothsubstance. Typical adhesive luting composites have elastic moduli ofabout 5 GPa (Journal of Prosthodontic Research 2010, 54, 59-64). Thus incase of a swelling of more than 0.25%, tensile stresses of more than12.5 MPa act on the adhesive bond. In case of swelling of more than0.3%, tensile stresses of more than 15 MPa operate. In case of higherswelling and higher tensile stresses associated therewith, the bondstrengths of the luting material are exceeded and loss of retentionoccurs.

In order to be able to provide securely retained and marginal gap-freeprosthetic restorations, it was thus the objective of the invention toobtain (as far as possible) swelling-free milling blanks.

In our own extensive studies, we were able to show that these materialsare accessible when their water sorption WSP is less than/equal to 18μg/mm³, measured according to ISO 4049 and their E modulus E greaterthan/equal to 13 GPa, measured according to the ADA specification No. 27and the quotient Q of WSP/E less than 1.35 μg/(GPa×mm³), preferably whentheir water sorption WSP is less than/equal to 15 μg/mm³, measuredaccording to ISO 4049 and their E modulus E greater than/equal to 15GPa, measured according to the ADA specification No. 27 and the quotientQ of WSP/E less than 1 μg/(GPa×mm³).

Dental milling blanks with the values stated above were hitherto unknownin the prior art (see Table 1 and FIG. 2).

Entirely surprisingly, we further found that the above conditions forobtaining (as far as possible) swelling-free or only minimally swellingpolymers can be achieved when the proportion by weight of ethoxylatedbisphenol-A dimethacrylate with an average degree of ethoxylation of 2to 4 ethoxy groups per molecule is greater than 40 weight percent andless than 50 weight percent of the quantity of radically polymerizablemonomers used and the total mass of inorganic fillers makes up at least83 weight percent of the total composition. This finding was not to beexpected since with a proven hydrophobic monomer such as HDDMA(hexanediol dimethacrylate) the above values for the water sorptioncould not be achieved. Those skilled in the art would have expected thatdue to the higher polarity of the ethoxy bond and the aromatic characterof the BPA ring structure, actually a higher water sorption would haveto take place compared to a purely aliphatic hydrocarbon skeleton suchas that of HDDMA, which is however not the case.

The present invention thus relates to a high performance compositeblock, more specifically a dental milling blank for the production ofpermanent indirect restorations in the CAD/CAM process, which ischaracterized in that it has a water sorption WSP of less than/equal to18 μg/mm³, measured according to ISO 4049 and an E modulus E greaterthan/equal to 13 GPa, measured according to the ADA specification No. 27and a quotient Q of WSP/E of less than 1.35 μg/(GPa×mm³), preferably hasa water sorption WSP of less than/equal to 15 μg/mm³, measured accordingto ISO 4049 and an E modulus E greater than/equal to 15 GPa, measuredaccording to the ADA specification No. 27 and a quotient Q of WSP/E ofless than 1 μg/(GPa×mm³) and which consists of the polymerizationproduct of a radically curable dental composition, which comprises

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the composition,

b) radically polymerizable monomers,

c) one or more initiators for radical curing and

d) optionally additives.

A preferred dental milling blank for the production of permanentindirect restorations in the CAD/CAM process which is characterized inthat it has a water sorption WSP of less than/equal to 18 μg/mm³,measured according to ISO 4049 and an E modulus E greater than/equal to13 GPa, measured according to the ADA specification No. 27 and aquotient Q of WSP/E of less than 1.35 μg/(GPa×mm³), preferably has awater sorption WSP of less than/equal to 15 μg/mm³, measured accordingto ISO 4049 and an E modulus E greater than/equal to 15 GPa, measuredaccording to the ADA specification No. 27 and a quotient Q of WSP/E ofless than 1 μg/(GPa×mm³) and which consists of the polymerizationproduct of a radically curable dental composition, which comprises

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the composition,

b) radically polymerizable monomers, which comprise bifunctional(meth)acrylates, wherein the proportion by weight of ethoxylatedbisphenol-A dimethacrylate with an average degree of ethoxylation of 2to 4 ethoxy groups per molecule is greater than 40% wt. % and less than50 wt. % of b),

c) one or more initiators for radically curing and

d) optionally additives.

A further preferred milling blank for the production of permanentindirect restorations in the CAD/CAM process is characterized in that ithas a water sorption WSP of less than/equal to 18 μg/mm³, measuredaccording to ISO 4049 and an E modulus E greater than/equal to 13 GPa,measured according to the ADA specification No. 27 and a quotient Q ofWSP/E of less than 1.35 μg/(GPa×mm³), preferably has a water sorptionWSP of less than/equal to 15 μg/mm³, measured according to ISO 4049 andan E modulus E greater than/equal to 15 GPa, measured according to theADA specification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which consists of the polymerization product of aradically curable dental composition, which comprises

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the composition, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm and

b) radically polymerizable monomers, which comprise bifunctional(meth)acrylates, wherein the proportion by weight of ethoxylatedbisphenol-A dimethacrylate with an average degree of ethoxylation of 2to 4 ethoxy groups per molecule is greater than 40% wt. % and less than50 wt. % of b) and

c) one or more initiators for radically curing and

d) optionally additives.

A quite preferred milling blank for the production of permanent indirectrestorations in the CAD/CAM process is characterized in that it has awater sorption WSP of less than/equal to 18 μg/mm³, measured accordingto ISO 4049 and an E modulus E greater than/equal to 13 GPa, measuredaccording to the ADA specification No. 27 and a quotient Q of WSP/E ofless than 1.35 μg/(GPa×mm³), preferably has a water sorption WSP of lessthan/equal to 15 μg/mm³, measured according to ISO 4049 and an E modulusE greater than/equal to 15 GPa, measured according to the ADAspecification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which consists of the polymerization product of aradically curable dental composition, which comprises

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the composition, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm,

wherein the glass composition a1) comprises a first glass compositiona1a) with a D50 value from 0.4-1.0 μm, preferably from 0.5-0.9 μm, and asecond glass composition a1b) with a D50 value from 1.2-5.0 μm,preferably from 1.5-4.0 μm, and wherein the mass ratio of a1a) to a1b)lies between 1:1.5 and 1:8, preferably between 1:2 to 1:5 and the massratio of a2) to the sum of a1a) and a1b) lies between 1:3 and 1:6 andthe ratio of the average particle size of the first microparticlefraction a1a) to the average particle size of the second microparticlefraction a1b) lies in the range from 1:1.5 to 1:10, preferably 1:2 to1:5, wherein the D75 value of a1a) is smaller than the D25 value of a1b)and

b) radically polymerizable monomers, which comprise bifunctional(meth)acrylates, wherein the proportion by weight of ethoxylatedbisphenol-A dimethacrylate with an average degree of ethoxylation of 2to 4 ethoxy groups per molecule is greater than 40% wt. % and less than50 wt. % of b) and

c) one or more initiators for radically curing and

d) optionally additives.

A particularly preferred milling blank for the production of permanentindirect restorations in the CAD/CAM process is characterized in that ithas a water sorption WSP of less than/equal to 18 μg/mm³, measuredaccording to ISO 4049 and an E modulus E greater than/equal to 13 GPa,measured according to the ADA specification No. 27 and a quotient Q ofWSP/E of less than 1.35 μg/(GPa×mm³), preferably has a water sorptionWSP of less than/equal to 15 μg/mm³, measured according to ISO 4049 andan E modulus E greater than/equal to 15 GPa, measured according to theADA specification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which consists of the polymerization product of aradically curable dental composition, which comprises

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the composition, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm,

wherein the glass composition comprises a1) a first glass compositiona1a) with a D50 value from 0.4-1.0 μm, preferably from 0.5-0.9 μm, and asecond glass composition a1b) with a D50 value from 1.2-5.0 μm,preferably from 1.5-4.0 μm, and wherein the mass ratio of a1a) to a1b)lies between 1:1.5 and 1:8, preferably between 1:2 to 1:5 and the massratio of a2) to the sum of a1a) and a1b) lies between 1:3 and 1:6 andthe ratio of the average particle size of the first microparticlefraction a1a) to the average particle size of the second microparticlefraction a1b) lies in the range from 1:1.5 to 1:10, preferably 1:2 to1:5,

wherein the D75 value of a1a) is smaller than the D25 value of a1b) andwherein the proportion of the non-aggregated and non-agglomeratedsilicic acid with an average particle size of not more than 80 nm a2) isgreater than 11.86 wt. % and less than 23 wt. %, based on the totalcomposition,

and

b) radically polymerizable monomers, which comprise bifunctional(meth)acrylates, wherein the proportion by weight of ethoxylatedbisphenol-A dimethacrylate with an average degree of ethoxylation of 2to 4 ethoxy groups per molecule is greater than 40% wt. % and less than50 wt. % of b), wherein the quantity of radically polymerizable monomersb) lies in a quantity range of at most 16.7 wt. %, based on the totalcomposition, and

c) one or more initiators for radically curing from 0.2 to 5 wt. %,based on the total composition, and

d) additives in a quantity range from 0.001 wt. % to 2 wt. %, based onthe total composition.

In other words, the present invention thus relates to a dental millingblank for the production of permanent indirect restorations in theCAD/CAM process, which is characterized in that it has a water sorptionWSP of less than/equal to 18 μg/mm³, measured according to ISO 4049 andan E modulus E greater than/equal to 13 GPa, measured according to theADA specification No. 27 and a quotient Q of WSP/E of less than 1.35μg/(GPa×mm³), preferably has a water sorption WSP of less than/equal to15 μg/mm³, measured according to ISO 4049 and an E modulus E greaterthan/equal to 15 GPa, measured according to the ADA specification No. 27and a quotient Q of WSP/E of less than 1 μg/(GPa×mm³) and which contains

a) inorganic fillers, wherein the total mass of the inorganic fillers isleast 83 wt. %, based on the total mass of the milling blank, and

b) polymerized fractions of radically polymerizable monomers.

In other words, the present invention thus relates to a preferred dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process, which is characterized in that it has a watersorption WSP of less than/equal to 18 μg/mm³, measured according to ISO4049 and an E modulus E greater than/equal to 13 GPa, measured accordingto the ADA specification No. 27 and a quotient Q of WSP/E of less than1.35 μg/(GPa×mm³), preferably has a water sorption WSP of lessthan/equal to 15 μg/mm³, measured according to ISO 4049 and an E modulusE greater than/equal to 15 GPa, measured according to the ADAspecification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which contains

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the milling blank, and

b) polymerized fractions of radically polymerizable monomers, whichcomprise bifunctional (meth)acrylates, wherein the proportion by weightof polymerized ethoxylated bisphenol-A dimethacrylate with an averagedegree of ethoxylation of 2 to 4 ethoxy groups per molecule is greaterthan 40% wt. % and less than 50 wt. % of b).

In other words, the present invention thus relates to a furtherpreferred milling blank for the production of permanent indirectrestorations in the CAD/CAM process, which is characterized in that ithas a water sorption WSP of less than/equal to 18 μg/mm³, measuredaccording to ISO 4049 and an E modulus E greater than/equal to 13 GPa,measured according to the ADA specification No. 27 and a quotient Q ofWSP/E of less than 1.35 μg/(GPa×mm³), preferably has a water sorptionWSP of less than/equal to 15 μg/mm³, measured according to ISO 4049 andan E modulus E greater than/equal to 15 GPa, measured according to theADA specification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and contains

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the milling blank, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm and

b) polymerized fractions of radically polymerizable monomers, whichcomprise bifunctional (meth)acrylates, wherein the proportion by weightof ethoxylated bisphenol-A dimethacrylate with an average degree ofethoxylation of 2 to 4 ethoxy groups per molecule is greater than 40%wt. % and less than 50 wt. % of b).

In other words, the present invention thus relates to a quite preferredmilling blank for the production of permanent indirect restorations inthe CAD/CAM process, which is characterized in that it has a watersorption WSP of less than/equal to 18 μg/mm³, measured according to ISO4049 and an E modulus E greater than/equal to 13 GPa, measured accordingto the ADA specification No. 27 and a quotient Q of WSP/E of less than1.35 μg/(GPa×mm³), preferably has a water sorption WSP of lessthan/equal to 15 μg/mm³, measured according to ISO 4049 and an E modulusE greater than/equal to 15 GPa, measured according to the ADAspecification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which contains

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the milling blank, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm,

wherein the glass composition a1) comprises a first glass compositiona1a) with a D50 value from 0.4-1.0 μm, preferably from 0.5-0.9 μm, and asecond glass composition a1b) with a D50 value from 1.2-5.0 μm,preferably from 1.5-4.0 μm, and wherein the mass ratio of a1a) to a1b)lies between 1:1.5 and 1:8, preferably between 1:2 to 1:5 and the massratio of a2) to the sum of a1a) and a1b) lies between 1:3 and 1:6 andthe ratio of the average particle size of the first microparticlefraction a1a) to the average particle size of the second microparticlefraction a1b) lies in the range from 1:1.5 to 1:10, preferably 1:2 to1:5,

wherein the D75 value of a1a) is smaller than the D25 value of a1b) and

b) polymerized fractions of radically polymerizable monomers, whichcomprise bifunctional (meth)acrylates, wherein the proportion by weightof ethoxylated bisphenol-A dimethacrylate with an average degree ofethoxylation of 2 to 4 ethoxy groups per molecule is greater than 40%wt. % and less than 50 wt. % of b).

In other words, the present invention thus relates to a particularlypreferred milling blank for the production of permanent indirectrestorations in the CAD/CAM process, which is characterized in that ithas a water sorption WSP of less than/equal to 18 μg/mm³, measuredaccording to ISO 4049 and an E modulus E greater than/equal to 13 GPa,measured according to the ADA specification No. 27 and a quotient Q ofWSP/E of less than 1.35 μg/(GPa×mm³), preferably has a water sorptionWSP of less than/equal to 15 μg/mm³, measured according to ISO 4049 andan E modulus E greater than/equal to 15 GPa, measured according to theADA specification No. 27 and a quotient Q of WSP/E of less than 1μg/(GPa×mm³) and which contains

a) inorganic fillers, wherein the total mass of the inorganic fillers isat least 83 wt. %, based on the total mass of the milling blank, andwherein the inorganic fillers a) comprise,

a1) a glass composition and

a2) non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm,

wherein the glass composition a1) comprises a first glass compositiona1a) with a D50 value from 0.4-1.0 μm, preferably from 0.5-0.9 μm, and asecond glass composition a1b) with a D50 value from 1.2-5.0 μm,preferably from 1.5-4.0 μm, and wherein the mass ratio of a1a) to a1b)lies between 1:1.5 and 1:8, preferably between 1:2 to 1:5 and the massratio of a2) to the sum of a1a) and a1b) lies between 1:3 and 1:6 andthe ratio of the average particle size of the first microparticlefraction a1a) to the average particle size of the second microparticlefraction a1b) lies in the range from 1:1.5 to 1:10, preferably 1:2 to1:5,

wherein the D75 value of a1a) is smaller than the D25 value of a1b) andwherein the proportion of the non-aggregated and non-agglomeratedsilicic acid with an average particle size of not more than 80 nm a2) isgreater than 11.86 wt. % and less than 23 wt. %, based on the totalcomposition,

b) polymerized fractions of radically polymerizable monomers, whichcomprise bifunctional (meth)acrylates, wherein the proportion by weightof ethoxylated bisphenol-A dimethacrylate with an average degree ofethoxylation of 2 to 4 ethoxy groups per molecule is greater than 40%wt. % and less than 50 wt. % of b), wherein the quantity of radicallypolymerizable monomers b) lies in a quantity range of at most 16.7 wt.%, based on the total composition.

a) Inorganic Fillers

The milling blank according to the invention comprises inorganic fillersin a quantity of at least 83 wt. %, based on the total composition. Theinorganic fillers are preferably used as mixtures. To optimize theproduct properties, the inorganic fillers are incorporated into thecompositions in different particle sizes, wherein they preferably have amultimodal, quite preferably a bimodal distribution.

As inorganic fillers, compact glasses and various silicic acids invarious sizes and states (monodisperse, polydisperse) can be used.

Suitable inorganic components are for example amorphous materials basedon mixed oxides made up of SiO₂, ZrO₂ and/or TiO₂ and fillers such asquartz glass ceramic or glass powder, barium silicate glasses, bariumfluorosilicate glasses, strontium silicate glasses, strontiumborosilicate, Li/Al silicate glasses, barium glasses, calcium silicates,sodium aluminum silicates, fluoroaluminosilicate glasses, oxides ofaluminum or silicon, zeolites, apatite, zirconium silicates, poorlysoluble metal salts such as barium sulfate or calcium fluoride andX-ray-opaque fillers such as ytterbium fluoride.

In a preferred embodiment, a milling blank according to the inventioncontains barium-aluminum borosilicate glasses.

For better incorporation into the polymer matrix, the fillers can beorganically surface-modified. By way of example, the surface treatmentof the fillers with a silane may be mentioned. Particularly suitable asa coupling agent is methacryloxypropyltrimethoxysilane.

In a preferred embodiment, a milling blank according to the inventioncontains surface-treated barium-aluminum borosilicate glasses,preferably silanized barium-aluminum borosilicate glasses and mostpreferably barium-aluminum borosilicate glasses treated withmethacryloxypropyltrimethoxysilane.

The milling blanks according to the invention can contain differentsilicic acids.

Preferably the milling blanks according to the invention containnanoscale silicic acids. The nanoscale silicic acids are particles withan average particle size of not more than 80 nm. The production of thenanoscale silicic acids is effected in known manner, e.g. by flamepyrolysis, plasma methods, gas phase condensation, colloid techniques,precipitation methods, sol-gel methods, etc.

In a preferred configuration, the nanoscale silicic acids are present innon-agglomerated and non-aggregated form, preferably in monodisperseform.

In order to enable good incorporation of the nanoparticles into thepolymer matrix of a radically curable dental composition, the surfacesof the nanoscale silicic acids are also organically surface-modified,i.e. their surfaces have organic structural elements. By way of example,the surface treatment of the fillers with a silane may be mentioned. Asthe coupling agent, methacryloxypropyltrimethoxysilane is alsoparticularly suitable here.

In a preferred embodiment, a milling blank according to the inventioncontains surface-treated nanoscale, non-agglomerated and non-aggregatedsilicic acid particles with an average particle size of not more than 80nm, preferably silanized nanoscale, non-agglomerated and non-aggregatedparticles with an average particle size of not more than 80 nm and mostpreferably nanoscale, non-agglomerated and non-aggregated silicic acidparticles with an average particle size of not more than 80 nm treatedwith methacryloxypropyltrimethoxysilane.

Commercially available nanoscale, non-agglomerated and non-aggregatedcolloidal silica sols which can be used are for example traded under thename “NALCO COLLOIDAL SILICAS” (Nalco Chemical Co.), “Ludox colloidalsilica” (Grace) or “Highlink OG” (Clariant).

In a preferred configuration, the filler content of the milling blankcomprises a mixture of a first filler a2) in the form ofnon-agglomerated, non-aggregated, organically surface-modifiednanoparticles with an average particle size less than 80 nm and a secondfiller a1) in the form of microparticles with an average particle sizein the range from 0.4 μm to 5 μm. Through the combination of a2)nanoparticles and a1) microparticles in the polymer matrix a completeand uniform volume filling of the composite material is achieved.

The content of organically surface-modified nanoparticles in a millingblank according to the invention with an average particle size less than80 nm is greater than 11.86 wt. % and less than 23 wt. %, based on thetotal composition. In our own studies, it was found that with a contentof 11.86 wt. % or less or with a content of 23 wt. % and more ofnon-agglomerated and non-aggregated, organically surface-modifiednanoparticles with an average particle size smaller than 80 nm themilling blank is no longer sufficiently swell-resistant.

Within the milling blank, the microparticles effect a largely uniformfilling of the volume, wherein the remaining cavities between themicroparticles are at least partially filled by the nanoparticlesdescribed above (component a2)). In connection with the presentinvention, microparticles are understood to be particles with an averageparticle size from 400 nm to 5 μm.

The microparticles of component a1) preferably have a bimodal particlesize distribution. Microparticles with a bimodal particle sizedistribution are preferred since with them a more complete volumefilling is achievable than with general use of microparticles ofmonomodal particle size distribution. In the presence of a bimodalparticle size distribution, the particles of the fractions with thelarger particle size effect a coarse filling of the volume, while theparticles of the fraction with the smaller particle size will as far aspossible fill the regions between the particles of the fractions withthe larger particle size. The cavities still remaining are filled bynanoparticles as described above.

The milling blank according to the invention comprises a component a1),which a first microparticle fraction a1a), which each possess an averageparticle size in the range from 0.4 μm to 1 μm, preferably from 0.5 μmto 0.9 μm and a second microparticle fraction a1b), which each possessan average particle size in the range from 1.2 μm to 5.0 μm, preferablyfrom 1.5 μm to 4.0 μm.

The ratio of the total mass of the first microparticle fraction to thetotal mass of the second microparticle fraction lies in the range from1:1.5 to 1:8, preferably in the range from 1:2 to 1:5.

b) Radically Polymerizable Monomers/Radically Polymerized Monomers

The dental milling blank according to the invention comprises contentsof radically polymerized monomers or radically polymerizable monomers ofthe polymerization product of a radically curable composition in aquantity of at most 16.7 wt. %, based on the total composition.

The radically polymerizable monomers of the polymerization product of aradically curable composition or the fractions of radically polymerizedmonomer can, without being limited thereto, be the (meth)acrylatemonomers usually used in composite materials in dental chemistry.

In the patent literature, a large number of compounds are mentioned (forexample also in DE 39 41 629 A1), all of which are diesters of acrylicor methacrylic acid and are suitable for use in a polymerization productof the present invention.

In a preferred embodiment, constituent (b) contains one or more monomersselected from the group consisting of ethylene glycol dimethacrylate(EGDMA), 1,6-hexanediol dimethacrylate (HDDMA), triethylene glycoldimethacrylate (TEGDMA), 1,10-decanediol dimethacrylate (DEDMA),1,12-dodecanediol dimethacrylate (DODMA), ethoxylated bisphenol-Adimethacrylate and ethoxylated bisphenol-A dimethacrylate, wherein thebisphenol is reacted with 2 to 4 moles ethylene oxide and theintermediate product is then saturated with 2 moles methacrylic acid,polyethylene glycol dimethacrylate (PEGDMA),7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-dioxydimethacrylate (UDMA), butanediol dimethacrylate, tetraethylene glycoldimethacrylate, neopentyl glycol dimethacrylate and bisphenol-A glycidylmethacrylate (bis-GMA).

Also usable are the corresponding dimethacrylates or diacrylates ofdihydroxymethyltricyclo[5.2.1.0^(2,6)]decane, as described in thepublications DE 1816823, DE 2419887, DE 2406557, DE 2931926, DE 3522005,DE 3522006, DE 3703120, DE 102005021332, DE 102005053775, DE102006060983, DE 69935794 and DE 102007034457.

c) Initiators

The milling blank according to the invention is producible either byradiative curing (photochemically) and/or by chemical curing (redoxreaction) and/or thermally. Thermal curing, which is for example broughtabout by peroxide decomposition, is preferred.

Examples of suitable photosensitizers are alpha-diketones, benzoin alkylethers, thioxanthones, benzophenones, acylphosphine oxides,acylgermanium compounds, acetophenones, ketals, titanocenes, sensitizingdyes, etc. The sensitizers can be used alone or in combination. Concreteexamples of substances of the different classes are to be found forexample in DE 10 2006 019 092 A1, or in DE 39 41 629 C2.

Examples of accelerators which are used together with the sensitizersare tertiary amines, secondary amines, barbituric acids, tin compounds,aldehydes and sulfur compounds. Concrete examples of substances of thedifferent classes are to be found in DE 10 2006 019 092 or in DE 39 41629 C2.

Further suitable initiators and initiator combinations are described inDE 601 16 142.

Suitable photoinitiators are characterized in that by absorption oflight in the wavelength range from 300 nm to 700 nm, preferably from 350nm to 600 nm and particularly preferably from 380 nm to 500 nm,optionally in combination with one or more coinitiators, they can effectthe curing of a radically curable dental composition.

The absorption maximum of camphorquinone (CQ) lies at ca. 470 nm andthus in the blue light range. Camphorquinone (CQ) is one of the PI₂initiators and is as a rule used together with a coinitiator.

A suitable catalyst system contains the combination of an alpha-diketoneand an aromatic tertiary amine, and the combination of camphorquinone(CQ) and ethyl p-N,N-dimethylaminobenzoate (DABE) is preferred.

Also preferred is the further combination of the system“alpha-diketone/aromatic tertiary amine” with a phosphine oxide, inparticular with phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide and/or2,4,6-trimethylbenzoyldiphenylphosphine oxide. Concerning the structureof suitable phosphine oxides, reference is made to the publications DE38 01 511 C2, DE 10 2006 050 153 A1, EP 0 184 095 B1, DE 42 31 579 C2,EP 0 366 977 B1, U.S. Pat. No. 7,081,485 B2, DE 32 36 026 A1, US2007/0027229 A1, EP 0 262 629 B1, EP 0 073 413, U.S. Pat. No. 7,148,382B2, U.S. Pat. No. 5,761,169, DE 197 08 294 A1, EP 0 057 474, EP 0 047902 A, EP 0 007 508, DE 600 29 481 T2, EP 0 980 682 B1, EP 0 948 955 B1,EP 1 236 459 B1 and EP 0 173 567 A2.

The phosphine oxides stated in these publications are particularlysuitable as a photopolymerization initiator system alone or incombination with the system “alpha-diketone/amine”.

Further suitable photoinitiators are described in J.-P. Fouassier,Photoinitiation, Photopolymerization and Photocuring, Hanser Publishers,Munich, Vienna, N.Y. 1995 and in J. F. Rabek (Ed.), Radiation Curing inPolymer Science and Technology, Vol. II, Elsevier Applied Science,London, N.Y. 1993.

Various initiators for chemical curing are known to those skilled in theart. By way of example, reference may be made to EP 1 720 506.Initiators for chemical curing are also described in the publicationsalready mentioned above DE 10 2006 019 092 and in DE 39 41 629.

Preferred initiators for chemical curing are dibenzoyl peroxide,dilauroyl peroxide, in particular dibenzoyl peroxide in combination withamines such as N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidineand structurally related amines.

Dual curing systems comprise a combination of photoinitiators andinitiators for chemical curing.

As well as the oxidatively acting organic peroxide compounds, as redoxsystems barbituric acids or barbituric acid derivatives andmalonylsulfamides can also be used.

Among the barbituric acid systems, the “Bredereck systems” are of greatimportance. Examples of suitable “Bredereck systems” and references tothe relevant patent literature are to be found in EP 1 839 640 and in DE1495520, WO 02/092021 or in WO 02/092023.

Instead of the barbituric acids, salts thereof can also be used.Examples of this are to be found in the following documents: EP 1 872767, EP 2 070 506, EP 1 881 010, DE 10 2007 050 763, U.S. Pat. No.6,288,138, DE 11 2006 001 049, U.S. Pat. No. 7,214,726 and EP 2 070 935.

Suitable malonylsulfamides are described in EP 0 059 451. Preferredcompounds here are 2,6-dimethyl-4-isobutylmalonylsulfamide,2,6-diisobutyl-4-propylmalonylsulfamide,2,6-dibutyl-4-propylmalonylsulfamide,2,6-dimethyl-4-ethylmalonylsulfamide and2,6-diocytyl-4-isobutylmalonylsulfamide.

Further, sulfur compounds in the oxidation state +2 or +4 such as sodiumbenzenesulfinate or sodium paratoluenesulfinate can be used.

To accelerate the curing, the polymerization can be performed in thepresence of compounds of heavy metals such as Ce, Fe, Cu, Mn, Co, Sn orZn, wherein copper compounds are particularly preferred. The heavy metalcompounds are preferably used in the form of soluble organic compounds.Preferred copper compounds here are copper benzoate, copper acetate,copper ethylhexanoate, copper di(methacrylate), copper acetylacetonateand copper naphthenate.

If peroxides are heated, they decompose and form free radicals which arecapable of starting the polymerization. The most widespread system forthermal polymerization is the use of dibenzoyl peroxide. Further thermalinitiators are ketone peroxides, peroxyketals, hydroperoxides, dialkylperoxides, diacyl peroxides, peroxy esters and peroxydicarbonates suchas dicumyl peroxide, chlorobenzoyl peroxide, t-butyl perbenzoate,dilauroyl peroxide, cumene hydroperoxide and tert.-butylperont3,5,5-trimethylhexanoate and azo compounds such as2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile,2,2′-azobis-1-cyclo-hexanecarbonitrile or dimethyl2,2′-azobisisobutyrate. Substances such as sodium or potassiumpersulfate also decompose thermally and are suitable compounds in thisrespect. These substances can be used singly or in mixtures with oneanother. For this, the radically curable compositions have merely to beheated to the decomposition temperature of the particular peroxidestated by the manufacturer. Advantageously, the radically curablecompositions are heated to a temperature above the decompositiontemperature and left there for some time, so that the polymerizationproduct has time for relaxation. Those skilled in the art find theoptimal temperature by successively increasing the temperature for thecuring up to the point at which the polymerization product displays nosignificant improvements in the important parameters measured on it suchas flexural strength, E modulus and water sorption.

Preferably the thermal curing is performed such that the radicallycurable composition is transferred into a block mold, where it is curedat temperatures from 80° C. to 150° C. and at a pressure from 100 to 300bar.

d) Additives

A milling blank according to the invention in many cases comprises oneor more further additive(s).

These additives can have various functions. Usual additives for use indental materials are known to those skilled in the art, and depending onthe desired function they will select the suitable additive(s). By wayof example, typical additives and their functions are described below.

UV absorbers, which are able to absorb UV radiation for example throughtheir conjugated double bond systems and aromatic rings, are in manycases a constituent of a milling blank according to the invention.Examples of UV absorbers are 2-hydroxy-4-methoxybenzophenone, phenylsalicylate, 3-(2′-hydroxy-5′-methylphenyl)benzotriazole or diethyl2,5-dihydroxyterephthalate. The polymers contain these additives inorder to ensure their color stability.

Since the teeth are to restored as realistically as possible, it isnecessary to provide dental milling blanks in a great variety ofcoloring. As a rule, inorganic dyes and organic pigments in very smallquantities are used for this purpose.

Further optional additives are dental medicaments and microbicides,preferably bactericides or fluorescent agents, which are also used inorder to reproduce the natural appearance of teeth.

The present invention further relates to a process for the production ofa milling blank for the production of permanent indirect restorations inthe CAD/CAM process characterized in that it has a water sorption WSP ofless than/equal to 18 μg/mm³, measured according to ISO 4049 and an Emodulus E greater than/equal to 13 GPa, measured according to the ADAspecification No. 27 and a quotient Q of WSP/E of less than 1.35μg/(GPa×mm³), and preferably has a water sorption WSP of less than/equalto 15 μg/mm³, measured according to ISO 4049 and an E modulus E greaterthan/equal to 15 GPa, measured according to the ADA specification No. 27and a quotient Q of WSP/E of less than 1 μg/(GPa×mm³) with the followingsteps:

-   -   providing radically polymerizable monomers.    -   providing inorganic fillers in a quantity of at least 83 wt. %,        based on the total mass of the composition,    -   providing a polymerization initiator,    -   optionally providing additives,    -   homogeneously mixing the components and    -   polymerizing the mixture.

After for example a crown has been milled from the blank in the CAD/CAMprocess and the tooth core has been prepared, the dentist willpreferably roughen the inner surface of the crown by sand-blasting, thenclean and prime it. He will then apply and cure the bonding onto thecore and finally fill a luting cement into the crown and place thelatter on the core.

Preferably, the milling blanks are thus used as a constituent of a kitaccording to the invention. The present invention thus also relates to akit, comprising

-   -   milling blanks according to the invention in different colors,    -   at least one primer,    -   at least one dental adhesive,    -   at least one luting cement and    -   optionally further accessories such as brushes, polishing agents        and mixing tips.

EXAMPLES

Abbreviations:

Bis-EMA2.6: Ethoxylated bisphenol A dimethacrylate with on average 2.6ethylene oxide units

Bis-EMA4: Ethoxylated bisphenol A dimethacrylate with on average 4ethylene oxide units

Bis-EMA6: Ethoxylated bisphenol A dimethacrylate with on average 6ethylene oxide units

Bis-EMA10: Ethoxylated bisphenol A dimethacrylate with on average 10ethylene oxide units

TCDDMA: Bis(methacryloyloxymethyhtricyclo[5.2.1.0^(2,6)]decane

UDMA:7,7,9-Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyldimethacrylate

TEGDMA: Triethylene glycol dimethacrylate

HDDMA: 1,6-Hexanediol dimethacrylate

DODMA: 1,12-Dodecanediol dimethacrylate

Dental glass 1: Barium-aluminum borosilicate glass (D50 0.8 μm/D25 0.5μm/D75 1.0 μm)

Dental glass 2: Barium-aluminum borosilicate glass (D50 2.7 μm/D25 1.4μm/D75 6.1 μm)

Dental glass 3: Barium-aluminum borosilicate glass (D50 1.1 μm/D25 0.7μm/D75 1.4 μm)

Dental glass 4: Barium-aluminum borosilicate glass (D50 1.4 μm/D25 1.1μm/D75 2.1 μm)

Dental glass 5: Barium-aluminum borosilicate glass (D50 1.4 μm/D25 0.8μm/D75 2.9 μm)

Nano-SiO₂: Non-agglomerated, non-aggregated silicic acid (D50 40 nm)

BPO: Dibenzoyl peroxide

Production of the Composite Pastes:

The individual components were weighed out according to the proportionsstated in Tables 2 to 13, homogenized for 30 minutes at 50 rpm on alaboratory kneader (PC Laborsystem, Magden CH) and then degassed on thelaboratory kneader for 15 minutes at 50 rpm and −0.85 bar.

Production of the Composite Blocks:

For the production of the composite blocks, the individual pastes werefilled into molds (15 mm×15 mm×20 mm). The curing was effectedisostatically at 250 bar and with the following temperature program (20°C.-2° C./min-120° C. (30 min)-5° C./min-20° C.).

Biaxial flexural strength (BBS): the biaxial flexural strength wasdetermined analogously to DIN EN ISO 6872:2009 (7.3.3). For this,firstly cylinders with a diameter of 14 mm were ground from thecomposite blocks in a 5-axis milling machine (250i, imes-icore GmbH).From these cylinders, disks with a thickness of 1.2 mm were thenproduced with a high-speed saw (IsoMet 4000, Buehler), deburred, groundand polished. The samples were loaded with a traverse velocity of 1mm/min up to fracture and the biaxial flexural strength calculatedaccording to the formula given in 7.3.3.4. As the Poisson ratio, a valueof 0.25 was used.

3-Point flexural strength (3PBS): the flexural strength was determinedanalogously to DIN EN ISO 6872:2009 (7.3.2) with span width of 12 mm anda support roller diameter of 2 mm. For this, from the composite blocks,test pieces with a breadth of 4 mm, a thickness of 1.2 mm and a lengthof 18 mm were produced with a high-speed saw (IsoMet 4000, Buehler),deburred, ground and polished. The samples were loaded with a traversevelocity of 1 mm/min up to fracture and the 3-point flexural strengthcalculated according to the formula given in 7.3.2.41.

Elastic modulus (E): The elastic modulus was determined analogously tothe calculation in ADA Spec. No. 27:1993 (7.8.4.2) as the slope of thestress-strain curve of the 3-point flexural strength determination inthe linear-elastic region.

$E = {\frac{3L}{4{bh}^{3}}\frac{\Delta\; F}{\Delta\; d}}$

L: span width

b: sample breadth

h: sample thickness

Δd: deformation in the linear-elastic region

ΔF: force change with a deformation Δd

Water sorption (W_(SP)): the water sorption was determined analogouslyto DIN EN ISO 4049:2010 (7.12). For this, from the composite blocks,test pieces with a length of 14.7 mm, a breadth of 14.7 mm and athickness of 0.5 mm were produced with a high-speed saw (IsoMet 4000,Buehler), deburred, ground and polished. The test pieces were dried toconstant mass in the desiccator at 37° C. and the mass (m₁) preciselydetermined to within 0.1 mg, and the length, the breadth and thethickness to within 0.01 mm. Next, the test pieces were stored for 7days at 37° C. in water. After 7 days, the test pieces were taken out,rinsed off with water, patted dry, swung backwards and forwards in airfor 15 seconds and, 1 minute after removal from the water, preciselyweighed to within 0.1 mg (m₂). After this weighing, the test pieces weredried to constant mass in the desiccator at 37° C. and the mass (m₃)determined to within 0.1 mg. The water sorption was calculated accordingto the formula stated in 7.12.4.1.

Linear swelling (LS): in a 5-axis milling machine (250i, imes-icoreGmbH) idealized crowns were produced as test pieces from the compositeblocks. These idealized crowns are hollow cylinders closed on one side(see FIG. 3). The height is 11 mm, the external diameter 12 mm and theinternal diameter 9 mm. This corresponds to a wall thickness of 1.5 mm.The thickness of the cover plate is 2 mm. Next, the crowns weredeburred, ground and polished. The test pieces were dried to constantmass in the desiccator at 37° C. and the internal diameter on thecylinder base determined precisely to within 0.001 mm at two mutuallyorthogonal points (L₁ and L₂). Next the test pieces were stored for 7days at 37° C. in water. After 7 days, the test pieces were taken out,rinsed off with water, patted dry, swung backwards and forwards in airfor 15 seconds and, 1 minute after removal from the water, the internaldiameter on the cylinder base determined precisely to within 0.001 mm atthe same two points as previously (L₃ and L₄). After the measurement,the test pieces were stored for a further 7 days at 37° C. in water.After this, the test pieces were taken out, dried as described above andthe internal diameter again determined precisely to within 0.001 mm atthe same two points as previously (L₅ and L₆). After the measurement,the test pieces were stored for a further 14 days at 37° C. in water.After this, the test pieces were taken out, dried as described above andthe internal diameter again determined precisely to within 0.001 mm atthe same two points as previously (L₇ and L₈). After the measurement,the test pieces were stored for a further 28 days at 37° C. in water.After this, the test pieces were taken out, dried as described above andthe internal diameter again determined precisely to within 0.001 mm atthe same two points as previously (L₉ and L₁₀). The linear swelling in %at the respective measurement times is obtained according to thefollowing formulae.

${{LS}_{1\mspace{14mu}{Week}}\mspace{14mu}\lbrack\%\rbrack} = {\frac{\frac{L_{3} + L_{4}}{2} - \frac{L_{1} + L_{2}}{2}}{\frac{L_{1} + L_{2}}{2}} \times 100\%}$${{LS}_{2\mspace{14mu}{Weeks}}\mspace{14mu}\lbrack\%\rbrack} = {\frac{\frac{L_{5} + L_{6}}{2} - \frac{L_{1} + L_{2}}{2}}{\frac{L_{1} + L_{2}}{2}} \times 100\%}$${{LS}_{4\mspace{14mu}{Weeks}}\mspace{14mu}\lbrack\%\rbrack} = {\frac{\frac{L_{7} + L_{8}}{2} - \frac{L_{1} + L_{2}}{2}}{\frac{L_{1} + L_{2}}{2}} \times 100\%}$${{LS}_{8\mspace{14mu}{Weeks}}\mspace{14mu}\lbrack\%\rbrack} = {\frac{\frac{L_{9} + L_{10}}{2} - \frac{L_{1} + L_{2}}{2}}{\frac{L_{1} + L_{2}}{2}} \times 100\%}$

Residue on ignition: for the determination of the residue on ignition,crucibles were heated for 10 hours at 150° C., allowed to cool to roomtemperature in the desiccator and then precisely weighed to within 0.1mg (m₁). Ca. 1 g of the respective composite block was broken up,crushed and precisely weighed to within 0.1 mg in the crucible (m₂).This was heated at 575° C. for 3 hours in the muffle furnace, then thecrucibles were allowed to cool to room temperature in the desiccator andthe mass was then precisely determined to within 0.1 mg (m₃). Theresidue on ignition was calculated according to the following formula.

${{residue}\mspace{14mu}{on}\mspace{14mu}{{ignition}\mspace{14mu}\lbrack\%\rbrack}} = {\frac{m_{3} - m_{1}}{m_{2}} \times 100\%}$

TABLE 1 Lava Ultimate Cerasmart Block HC Crios (3M Espe) (GC) (Shofu)(Coltene) Filler content 80 70.7 (manufacturer information) [%] Residueon ignition [%] 73 65 62 70 Biaxial flexural 174 214 147 232 strength[MPa] 3-Point flexural 163 159 122 198 strength [MPa] E modulus [GPa]11.8 9.9 8.7 12.7 WSP [μg/mm³] 36 29 40 23 WSP/E 3.05 2.93 4.60 1.81[μg/(GPa × mm³)] LS (1 week) [%] 0.23% 0.19% 0.27% 0.15% LS (2 weeks)[%] 0.42% 0.36% 0.48% 0.27% LS (4 weeks) [%] 0.51% 0.42% 0.60% 0.34% LS(8 weeks) [%] 0.53% 0.44% 0.63% 0.35%

TABLE 2 Example 1 2 3 4 Filler (a) (a1a) Dental 13.00 13.00 13.00 13.00glass 1 (a1b) Dental 57.50 57.50 57.50 57.50 glass 2 Dental glass 3Dental glass 4 Dental glass 5 (a2) Nano-SiO₂ 15.00 15.00 15.00 15.00 (40nm) Total (a) 85.50 85.50 85.50 85.50 Monomers (b1a) Bis- 6.00 6.00 6.006.50 (b) EMA2.6 Bis-EMA4 (b1b) Bis-EMA6 Bis- EMA10 (b2) TCDDMA 3.75 5.002.50 3.50 UDMA 3.75 2.50 5.00 3.50 HDDMA 0.70 0.70 0.70 0.70 DODMATEGDMA Total (b) 14.20 14.20 14.20 14.20 Initiators (c) BPO 0.30 0.300.30 0.30 Total 100.00 100.00 100.00 100.00

TABLE 3 Example 1 2 3 4 (a1a)/(a1b) 0.23 0.23 0.23 0.23 (a2)/[(a1a) +(a1b)] 0.21 0.21 0.21 0.21 (b1a)/(b) × 100% 42.3% 42.3% 42.3% 45.8%Biaxial flexural 301 269 292 284 strength [MPa] 3-Point flexural 274 241266 259 strength [MPa] E modulus [GPa] 18.3 15.8 18.6 16.4 WSP [μg/mm³]13 11 15 12 WSP/E 0.71 0.70 0.81 0.73 [μg/(GPa × mm³)] LS (1 week) [%]0.09% 0.09% 0.10% 0.08% LS (2 weeks) [%] 0.15% 0.14% 0.16% 0.13% LS (4weeks) [%] 0.19% 0.18% 0.19% 0.17% LS (8 weeks) [%] 0.19% 0.19% 0.20%0.18%

TABLE 4 Example 5 6 7 8 Filler (a) (a1a) Dental 13.00 13.00 13.00 13.00glass 1 (a1b) Dental 57.50 57.50 57.50 57.50 glass 2 Dental glass 3Dental glass 4 Dental glass 5 (a2) Nano-SiO₂ 15.00 15.00 15.00 15.00 (40nm) Total (a) 85.50 85.50 85.50 85.50 Monomers (b1a) Bis- 7.00 5.80 6.006.00 (b) EMA2.6 Bis-EMA4 (b1b) Bis-EMA6 Bis- EMA10 (b2) TCDDMA 3.25 3.853.75 3.75 UDMA 3.25 3.85 3.75 3.75 HDDMA 0.70 0.70 0.70 DODMA 0.70TEGDMA 0.70 Total (b) 14.20 14.20 14.20 14.20 Initiators (c) BPO 0.300.30 0.30 0.30 Total 100.00 100.00 100.00 100.00

TABLE 5 Example 5 6 7 8 (a1a)/(a1b) 0.23 0.23 0.23 0.23 (a2)/[(a1a) +(a1b)] 0.21 0.21 0.21 0.21 (b1a)/(b) × 100% 49.3% 40.8% 42.3% 42.3%Biaxial flexural 271 295 261 299 strength [MPa] 3-Point flexural 251 270237 271 strength [MPa] E modulus [GPa] 15.1 18.7 15.1 19.1 WSP [μg/mm³]13 15 11 14 WSP/E 0.86 0.80 0.73 0.73 [μg/(GPa × mm³)] LS (1 week) [%]0.09% 0.09% 0.05% 0.07% LS (2 weeks) [%] 0.18% 0.17% 0.11% 0.13% LS (4weeks) [%] 0.21% 0.20% 0.17% 0.16% LS (8 weeks) [%] 0.22% 0.21% 0.19%0.17%

TABLE 6 11 12 Example 9 10 (Comparison) (Comparison) Filler (a) (a1a)Dental glass 1 13.00 13.00 13.00 (a1b) Dental glass 2 70.50 57.50 57.5057.50 Dental glass 3 Dental glass 4 Dental glass 5 (a2) Nano-SiO₂ 15.0015.00 15.00 15.00 (40 nm) Total (a) 85.50 85.50 85.50 85.50 Monomers(b1a) Bis-EMA2.6 6.00 (b) Bis-EMA4 6.00 (b1b) Bis-EMA6 6.00 Bis-EMA106.00 (b2) TCDDMA 3.75 3.75 3.75 3.75 UDMA 3.75 3.75 3.75 3.75 HDDMA 0.700.70 0.70 DODMA TEGDMA Total (b) 14.20 14.20 14.20 14.20 Initiators (c)BPO 0.30 0.30 0.30 0.30 Total 100.00 100.00 100.00 100.00

TABLE 7 11 12 Example 9 10 (Comparison) (Comparison) (a1a)/(a1b) 0.000.23 0.23 0.23 (a2)/[(a1a) + (a1b)] 0.21 0.21 0.21 0.21 (b1a)/(b) × 100%42.3% 42.3% 0.0% 0.0% Biaxial flexural 256 289 262 219 strength [MPa]3-Point flexural 221 262 239 198 strength [MPa] E modulus [GPa] 13.417.7 13.7 12.6 WSP [μg/mm³] 18 15 19 26 WSP/E [μg/(GPa × mm³)] 1.34 0.851.39 2.06 LS (1 week) [%] 0.13% 0.10% 0.15% 0.17% LS (2 weeks) [%] 0.22%0.16% 0.27% 0.29% LS (4 weeks) [%] 0.28% 0.21% 0.31% 0.36% LS (8 weeks)[%] 0.28% 0.22% 0.32% 0.38%

TABLE 8 14 15 16 Example 13 (Comparison) (Comparison) (Comparison)Filler (a) (a1a) Dental glass 1 12.70 12.40 13.00 12.40 (a1b) Dentalglass 2 56.10 54.70 57.50 54.70 Dental glass 3 Dental glass 4 Dentalglass 5 (a2) Nano-SiO₂ 14.60 14.20 15.00 14.20 (40 nm) Total (a) 83.4081.30 85.50 81.30 Monomers (b1a) Bis-EMA2.6 6.90 7.80 5.00 6.40 (b)Bis-EMA4 (b1b) Bis-EMA6 Bis-EMA10 (b2) TCDDMA 4.30 4.85 3.75 6.00 UDMA4.30 4.85 3.75 6.00 HDDMA 0.80 0.90 1.70 DODMA TEGDMA Total (b) 16.3018.40 14.20 18.40 Initiators (c) BPO 0.30 0.30 0.30 0.30 Total 100.00100.00 100.00 100.00

TABLE 9 14 15 16 Example 13 (Comparison) (Comparison) (Comparison)(a1a)/(a1b) 0.23 0.23 0.23 0.23 (a2)/[(a1a) + (a1b)] 0.21 0.21 0.21 0.21(b1a)/(b) × 100% 42.3% 42.4% 35.2% 34.8% Biaxial flexural 266 201 189203 strength [MPa] 3-Point flexural 240 175 169 177 strength [MPa] Emodulus [GPa] 16.7 13.7 11.8 12.1 WSP [μg/mm³] 15 19 16 17 WSP/E[μg/(GPa × mm³)] 0.90 1.39 1.36 1.40 LS (1 week) [%] 0.10% 0.16% 0.14%0.14% LS (2 weeks) [%] 0.17% 0.26% 0.24% 0.26% LS (4 weeks) [%] 0.23%0.31% 0.32% 0.31% LS (8 weeks) [%] 0.23% 0.31% 0.32% 0.32%

TABLE 10 17 18 20 Example (Comparison) (Comparison) 19 (Comparison)Filler (a) (a1a) Dental glass 1 13.00 12.40 12.70 12.40 (a1b) Dentalglass 2 57.50 Dental glass 3 54.70 Dental glass 4 56.10 Dental glass 556.10 (a2) Nano-SiO₂ 15.00 14.20 14.60 14.60 (40 nm) Total (a) 85.5081.30 83.40 83.40 Monomers (b1a) Bis-EMA2.6 7.50 7.80 6.90 6.90 (b)Bis-EMA4 (b1b) Bis-EMA6 Bis-EMA10 (b2) TCDDMA 3.00 4.85 4.30 4.30 UDMA3.00 4.85 4.30 4.30 HDDMA 0.70 0.90 0.80 0.80 DODMA TEGDMA Total (b)14.20 18.40 16.30 16.30 Initiators (c) BPO 0.30 0.30 0.30 0.30 Total100.00 100.00 100.00 100.00

TABLE 11 17 18 20 Example (Comparison) (Comparison) 19 (Comparison)(a1a)/(a1b) 0.23 0.23 0.23 0.23 (a2)/[(a1a) + (a1b)] 0.21 0.21 0.21 0.21(b1a)/(b) × 100% 52.8% 42.4% 42.3% 42.3% Biaxial flexural 198 213 265231 strength [MPa] 3-Point flexural 177 194 242 211 strength [MPa] Emodulus [GPa] 11.0 14.4 14.7 12.5 WSP [μg/mm³] 15 20 16 17 WSP/E[μg/(GPa × mm³)] 1.36 1.39 1.09 1.36 LS (1 week) [%] 0.16% 0.18% 0.12%0.14% LS (2 weeks) [%] 0.25% 0.27% 0.19% 0.23% LS (4 weeks) [%] 0.30%0.31% 0.25% 0.30% LS (8 weeks) [%] 0.31% 0.31% 0.26% 0.31%

TABLE 12 21 22 23 24 Example (Comparison) (Comparison) (Comparison)(Comparison) Filler (a) (a1a) Dental glass 1 35.25 7.00 10.00 13.92(a1b) Dental glass 2 35.25 60.10 44.20 61.58 Dental glass 3 Dental glass4 Dental glass 5 (a2) Nano-SiO₂ 15.00 14.20 25.00 10.00 (40 nm) Total(a) 85.50 81.30 79.20 85.50 Monomers (b1a) Bis-EMA2.6 6.00 7.80 8.706.00 (b) Bis-EMA4 (b1b) Bis-EMA6 Bis-EMA10 (b2) TCDDMA 3.76 4.85 5.403.75 UDMA 3.75 4.85 5.40 3.75 HDDMA 0.70 0.90 1.00 0.70 DODMA TEGDMATotal (b) 14.20 18.40 20.50 14.20 Initiators (c) BPO 0.30 0.30 0.30 0.30Total 100.00 100.00 100.00 100.00

TABLE 13 21 22 23 24 Example (Comparison) (Comparison) (Comparison)(Comparison) (a1a)/(a1b) 1.00 0.12 0.23 0.23 (a2)/[(a1a) + (a1b)] 0.210.21 0.46 0.13 (b1a)/(b) × 100% 42.3% 42.4% 42.4% 42.3% Biaxial flexural204 197 156 188 strength [MPa] 3-Point flexural 181 174 128 145 strength[MPa] E modulus [GPa] 11.7 14.3 11.7 12.4 WSP [μg/mm³] 19 21 31 21 WSP/E[μg/(GPa × mm³)] 1.62 1.47 2.65 1.69 LS (1 week) [%] 0.19% 0.20% 0.23%0.21% LS (2 weeks) [%] 0.27% 0.26% 0.37% 0.29% LS (4 weeks) [%] 0.32%0.31% 0.43% 0.34% LS (8 weeks) [%] 0.33% 0.32% 0.45% 0.35%

The invention claimed is:
 1. A dental milling blank for the productionof permanent indirect restorations in the CAD/CAM process, said dentalmilling blank having a water sorption WSP of less than or equal to 18μg/mm³ measured according to ISO 4049 and an elastic modulus E greaterthan or equal to 13 GPa, measured according to the ADA specification No.27 and a quotient Q of WSP/E of less than 1.35 μg/(GPa×mm³) and consistsof the polymerization product of a radically curable dental composition,which comprises a) inorganic fillers, wherein the total mass of theinorganic fillers is at least 83 wt. %, based on the total mass of thecomposition, wherein the inorganic fillers a) comprise a1) a glasscomposition comprising a bimodal particle size distribution, and a2)non-aggregated and non-agglomerated silicic acid with an averageparticle size of not more than 80 nm, b) radically polymerizablemonomers, c) one or more initiators for radically curing, wherein theglass composition a1) comprises a first glass composition a1a) with aD50 value from 0.4-1.0 μm, and a second glass composition a1b) with aD50 value from 1.2-5.0 μm.
 2. The dental milling blank for theproduction of permanent indirect restorations in the CAD/CAM process asclaimed in claim 1, wherein the dental milling blank has a watersorption WSP of less than/equal to 15 μg/mm³, measured according to ISO4049 and an elastic modulus E greater than/equal to 15 GPa, measuredaccording to the ADA specification No. 27 and a quotient Q of WSP/E ofless than 1 μg/(GPa×mm³).
 3. The dental milling blank for the productionof permanent indirect restorations in the CAD/CAM process as claimed inclaim 1, wherein the inorganic fillers a) are organicallysurface-coated.
 4. The dental milling blank for the production ofpermanent indirect restorations in the CAD/CAM process as claimed inclaim 3, wherein the inorganic fillers a) are silanized.
 5. The dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process as claimed in claim 3, wherein the inorganic fillersa) are treated with methacryloxypropyltrimethoxysilane.
 6. The dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process as claimed in one of claim 1, wherein the glasscomposition a1) is a barium-aluminum borosilicate composition.
 7. Thedental milling blank for the production of permanent indirectrestorations in the CAD/CAM process as claimed in claim 1, wherein amass ratio of a1a) to a1b) lies between 1:1.5 and 1:8.
 8. The dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process as claimed in claim 1, wherein the glass compositiona1) comprises the first glass composition a1a) with a D50 value from0.5-0.9 μm, and the second glass composition a1b) with a D50 value from1.5-4.0 μm.
 9. The dental milling blank for the production of permanentindirect restorations in the CAD/CAM process as claimed in claim 8,wherein a mass ratio of a1a) to a1b) lies between 1:1.5 and 1:8.
 10. Thedental milling blank for the production of permanent indirectrestorations in the CAD/CAM process as claimed in claim 1, wherein thecontent of the non-aggregated and non-agglomerated silicic acid with anaverage particle size of not more than 80 nm is greater than 11.86 wt. %and less than 23 wt. %, based on the total composition.
 11. The dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process as claimed in claim 1, wherein the radicallypolymerizable monomers b) comprise bifunctional (meth)acrylates andwherein the proportion by weight of ethoxylated bisphenol-Adimethacrylate with an average degree of ethoxylation of 2 to 4 ethoxygroups per molecule is greater than 40% wt. % and less than 50 wt. % ofb).
 12. The dental milling blank for the production of permanentindirect restorations in the CAD/CAM process as claimed in claim 1,wherein the quantity of radically polymerizable monomers b) lies in arange of at most 16.7 wt. %, based on the total composition, and thequantity of one or more initiator(s) for radically curing c) lies in arange from 0.2 to 5 wt. %, based on the total composition, and thequantity of the additive or additives d) lies in a range from 0.001 wt.% to 2 wt. %, based on the total composition.
 13. The dental millingblank for the production of permanent indirect restorations in theCAD/CAM process as claimed in claim 1, wherein the radically curablecomposition additionally comprises additives d).
 14. A process for theproduction of a dental milling blank as claimed in claim 1 with thefollowing steps: providing the constituents a), b), and c),homogeneously mixing the constituents and curing the constituents.
 15. Akit, comprising several dental milling blanks as claimed in claim 10 indifferent colors, at least one primer, at least one dental adhesive, atleast one luting cement and optionally further accessories such asbrushes, polishing agents and mixing tips.
 16. A dental milling blankfor the production of permanent indirect restorations in the CAD/CAMprocess, said dental milling blank having a water sorption WSP of lessthan or equal to 18 μg/mm³ measured according to ISO 4049 and an elasticmodulus E greater than or equal to 13 GPa, measured according to the ADAspecification No. 27 and a quotient Q of WSP/E of less than 1.35μg/(GPa×mm³) and consists of the polymerization product of a radicallycurable dental composition, which comprises a) inorganic fillers,wherein the total mass of the inorganic fillers is at least 83 wt. %,based on the total mass of the composition, wherein the inorganicfillers a) comprise a1) a glass composition comprising a bimodalparticle size distribution, and a2) non-aggregated and non-agglomeratedsilicic acid with an average particle size of not more than 80 nm, b)radically polymerizable monomers, c) one or more initiators forradically curing, wherein the glass composition a1) comprises a firstglass composition a1a) and a second glass composition a1b), wherein theD75 value of a1a) is smaller than the D25 value of a1b).
 17. The dentalmilling blank for the production of permanent indirect restorations inthe CAD/CAM process as claimed in claim 16, wherein the dental millingblank has a water sorption WSP of less than/equal to 15 μg/mm³, measuredaccording to ISO 4049 and an elastic modulus E greater than/equal to 15GPa, measured according to the ADA specification No. 27 and a quotient Qof WSP/E of less than 1 μg/(GPa×mm³).
 18. The dental milling blank forthe production of permanent indirect restorations in the CAD/CAM processas claimed in claim 16, wherein a mass ratio of a1a) to a1b) liesbetween 1:1.5 and 1:8.
 19. The dental milling blank for the productionof permanent indirect restorations in the CAD/CAM process as claimed inclaim 16, wherein a mass ratio of a2) to the sum of a1a) and a1b) liesbetween 1:3 and 1:6.
 20. The dental milling blank for the production ofpermanent indirect restorations in the CAD/CAM process as claimed inclaim 16, wherein a ratio of the average particle she of first glasscomposition a1a) to the average particle size of second glasscomposition a1b) lies in the range from 1:1.5 to 1:10.